US4658011A - Polymerization of oxazoline using alkali or alkaline earth metal complex catalyst - Google Patents
Polymerization of oxazoline using alkali or alkaline earth metal complex catalyst Download PDFInfo
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- US4658011A US4658011A US06/765,634 US76563485A US4658011A US 4658011 A US4658011 A US 4658011A US 76563485 A US76563485 A US 76563485A US 4658011 A US4658011 A US 4658011A
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 title claims description 18
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims description 12
- 239000003513 alkali Substances 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005011 alkyl ether group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005013 aryl ether group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 150000002918 oxazolines Chemical class 0.000 abstract description 11
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 alkyl triflate Chemical compound 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000004593 Epoxy Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GKPDXYQIQIJZJT-UHFFFAOYSA-N 2-benzyl-4,5-dihydro-1,3-oxazole Chemical compound C=1C=CC=CC=1CC1=NCCO1 GKPDXYQIQIJZJT-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011951 cationic catalyst Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- SBMMYMGTYKAHTE-UHFFFAOYSA-N 2-(1-chlorohexyl)oxirane Chemical compound CCCCCC(Cl)C1CO1 SBMMYMGTYKAHTE-UHFFFAOYSA-N 0.000 description 1
- HTJFSXYVAKSPNF-UHFFFAOYSA-N 2-[2-(oxiran-2-yl)ethyl]oxirane Chemical compound C1OC1CCC1CO1 HTJFSXYVAKSPNF-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- QZAJJEFYEVWODE-UHFFFAOYSA-N methyl 8-[3-[(3-pentyloxiran-2-yl)methyl]oxiran-2-yl]octanoate Chemical compound CCCCCC1OC1CC1C(CCCCCCCC(=O)OC)O1 QZAJJEFYEVWODE-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
Definitions
- This invention relates to a process for the homopolymerization of mono- and bis-oxazolines in the presence of a catalyst comprising an alkali metal or an alkaline earth metal cationic complex.
- Oxazolines have been known to undergo ring opening homopolymerization in the presence of catalysts such as Lewis acids, inorganic acids, and cationic catalysts such as boron trifluoride etherate, see Chem. Revs. 71, 483 (1971). It has also been shown by Kobayashi et al, Makromol. Chem., 185, 441 (1984) that alkyl triflate or alkyl tosylate will catalyze the homopolymerization of oxazolines. The use of cationic complexes of alkali and alkaline earth metals as catalysts in the homopolymerization of oxazolines has not been disclosed in the prior art. The ring opening copolymerization of oxazolines and epoxy compounds using these catalysts also has not previously been disclosed.
- catalysts such as Lewis acids, inorganic acids, and cationic catalysts such as boron trifluoride etherate, see Chem. Revs. 71, 483 (1971). It has also
- R represents hydrogen, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 12 carbon atoms, an alkaryl group having from 7 to 20 carbon atoms, an alkyl ether group having from 1 to 20 carbon atoms or an aryl ether group having from 6 to 26 carbon atoms.
- R' represents an alkylene group having from 1 to 20 carbon atoms, an arylene group having from 6 to 12 carbon atoms or an alkylene ether group having from 2 to 20 carbon atoms.
- the catalysts embodied in the process of this invention include those conforming to the type M(X) n wherein M represents an alkali or an alkaline earth metal, X represents BF 4 , PF 6 , BPh 4 , ClO 4 , AsF 6 and SbF 6 , and n represents 1 or 2 depending on the valence of M.
- Epoxy resins which are useful in this invention can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and they may be substitutes if desired with other substituents besides the epoxy groups, e.g., hydroxyl groups, ether radicals, halogen atoms, and the like.
- Typical epoxy components suitable if the practice of this invention include those disclosed in U.S. Pat. Nos. 2,500,600 and 2,374,483 which are incorporated here by reference.
- Preferred in this invention are 1,2-epoxy compounds having an epoxide equivalence greater than 1, that is to say, compounds containing more than one group of this formula ##STR3##
- the 1,2-epoxide groups may be either terminal or inner ones. Particularly suitable terminal 1,2-epoxide groups are 1,2-epoxy ethyl or 1,2-epoxy propyl groups. The latter may be linked to an oxygen atom, that is to say, they are glycidyl ether or glycidyl ester groups. Compounds with inner epoxide groups usually contain the 1,2-epoxide group in an aliphatic chain or in a cycloaliphatic ring.
- epoxy compounds containing an inner 1,2-epoxy group there are suitable epoxidized diolefins, dienes, or cyclic dienes, such as 1,2,5,6-diepoxy hexane, 1,2,4,5-diepoxy cyclohexane, dicyclopentadiene diepoxide, dipentene diepoxide, and vinyl cyclohexene diepoxide, epoxidized diolefinically unsaturated carboxylic acid esters, such as methyl-9,10,12,13-diepoxy stearate, or the dimethyl ester of 6,7,10,11-diepoxyhexadecane-1,16-dicarboxylic acid.
- epoxidized diolefins, dienes, or cyclic dienes such as 1,2,5,6-diepoxy hexane, 1,2,4,5-diepoxy cyclohexane, dicyclopentadiene diepoxide, dipentene diepoxide, and
- epoxidized mono-, di-, or polyesters mono-, di-, or poly acetals containing at least one cycloaliphatic 5-membered or 6-membered ring, to which at least two 1,2-epoxide groups are linked.
- a widely used class of polyepoxides which can be used in the present invention are the epoxy polyethers obtained by reacting a halogen containing epoxide or dihalohydrin, such as epichlorohydrin, epibromohydrin, 3-chloro-1,2-epoxyoctane, and the like with either a polyhydric phenol or a polyhydric alcohol.
- a halogen containing epoxide or dihalohydrin such as epichlorohydrin, epibromohydrin, 3-chloro-1,2-epoxyoctane, and the like
- the process of this invention can be carried out with or without a solvent at a temperature in the range of from about 80 degrees C. to about 200 degrees C. at a pressure in the range of from about atmospheric to about 50 atmospheres.
- the amounts of the cationic catalysts useful in the polymerization of oxazolines and in the copolymerization of oxazolines with epoxy resins may be in the range of 0.1 to about 5% by weight of catalyst based on the weight of the monomer or monomers.
- the polymerizations can be carried out by using either the solid catalyst which generally dissolves in the liquid oxazolines or solutions of catalyst in solvents such as alcohols, dialkyl ketones, linear and cyclic ethers and the like.
- Liquid benzyl oxazoline (Formula I wherein R is benzyl) (10 g) and 0.2 g of lithium fluoborate were mixed and heated at 120 degrees C. for one hour during which time the liquid benzyl oxazoline polymerized to give a solid polymer which was soluble in dimethyl formamide and N-methyl pyrrolidone.
- the Tg by DSC (Differential Scanning Calorimetry) for this polymer was found to be 69 degrees C. and 10% weight loss in nitrogen by TGA (Thermo Gravimetric Analysis) occurred at 358 degrees C.
- a mixture of 2.5 g of an oxazoline of Formula I in which R is ethyl, 0.5 g of the bis-oxazoline described in Example 2 and 0.05 g of lithium fluoborate was prepared at room temperature and heated at 120 degrees C. for one hour during which time solid polymer formed.
- the Tg for the polymer by DSC was found to be 40.3 degrees C. and 10% weight loss in nitrogen by TGA occurred at 388 degrees C.
- Example 3 The procedure of Example 3 was followed using 2.5 g of the benzyl oxazoline of Example 1, 0.35 g of the bis-oxazoline of Example 2 and 0.05 g of lithium fluoborate. The resulting polymer was found to have a Tg of 64.1 degrees C. and 10% weight loss occurred at 355 degrees C.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A process for the polymerization of oxazolines and copolymerization of oxazolines with epoxy resins in the presence of catalytic amounts of cationic complexes of alkali metals and alkaline earth metals is disclosed.
Description
This invention relates to a process for the homopolymerization of mono- and bis-oxazolines in the presence of a catalyst comprising an alkali metal or an alkaline earth metal cationic complex.
Oxazolines have been known to undergo ring opening homopolymerization in the presence of catalysts such as Lewis acids, inorganic acids, and cationic catalysts such as boron trifluoride etherate, see Chem. Revs. 71, 483 (1971). It has also been shown by Kobayashi et al, Makromol. Chem., 185, 441 (1984) that alkyl triflate or alkyl tosylate will catalyze the homopolymerization of oxazolines. The use of cationic complexes of alkali and alkaline earth metals as catalysts in the homopolymerization of oxazolines has not been disclosed in the prior art. The ring opening copolymerization of oxazolines and epoxy compounds using these catalysts also has not previously been disclosed.
I have discovered that oxazolines of Formula I and bis-oxazolines of Formula II will undergo ring opening homopolymerization in the presence of cationic complex catalysts of alkali and alkaline earth metals. ##STR1## In Formula I R represents hydrogen, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 12 carbon atoms, an alkaryl group having from 7 to 20 carbon atoms, an alkyl ether group having from 1 to 20 carbon atoms or an aryl ether group having from 6 to 26 carbon atoms. In Formula II R' represents an alkylene group having from 1 to 20 carbon atoms, an arylene group having from 6 to 12 carbon atoms or an alkylene ether group having from 2 to 20 carbon atoms.
The catalysts embodied in the process of this invention include those conforming to the type M(X)n wherein M represents an alkali or an alkaline earth metal, X represents BF4, PF6, BPh4, ClO4, AsF6 and SbF6, and n represents 1 or 2 depending on the valence of M.
In the process of this invention mono-oxazolines polymerize rapidly in the presence of the catalyst to give solid thermoplastic polymers and the bis-oxazolines polymerize rapidly to give solid thermoset polymers, both types of polymers containing polyamide groups. Thus, when a mono-oxazoline, e.g., ethyl oxazoline, is mixed with about 2% by weight of lithium fluoborate and the mixture is heated at 110 degrees C., rapid polymerization occurs giving a solid polymer which contains a strong infrared band at 1620 cm-1 due to amide groups present. This reaction is illustrated in the following equation. ##STR2##
The process of this invention can also be applied to the copolymerization of oxazolines and epoxy resins. Epoxy resins which are useful in this invention can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and they may be substitutes if desired with other substituents besides the epoxy groups, e.g., hydroxyl groups, ether radicals, halogen atoms, and the like. Typical epoxy components suitable if the practice of this invention include those disclosed in U.S. Pat. Nos. 2,500,600 and 2,374,483 which are incorporated here by reference. Preferred in this invention are 1,2-epoxy compounds having an epoxide equivalence greater than 1, that is to say, compounds containing more than one group of this formula ##STR3##
The 1,2-epoxide groups may be either terminal or inner ones. Particularly suitable terminal 1,2-epoxide groups are 1,2-epoxy ethyl or 1,2-epoxy propyl groups. The latter may be linked to an oxygen atom, that is to say, they are glycidyl ether or glycidyl ester groups. Compounds with inner epoxide groups usually contain the 1,2-epoxide group in an aliphatic chain or in a cycloaliphatic ring.
As epoxy compounds containing an inner 1,2-epoxy group there are suitable epoxidized diolefins, dienes, or cyclic dienes, such as 1,2,5,6-diepoxy hexane, 1,2,4,5-diepoxy cyclohexane, dicyclopentadiene diepoxide, dipentene diepoxide, and vinyl cyclohexene diepoxide, epoxidized diolefinically unsaturated carboxylic acid esters, such as methyl-9,10,12,13-diepoxy stearate, or the dimethyl ester of 6,7,10,11-diepoxyhexadecane-1,16-dicarboxylic acid. Furthermore, there may be mentioned epoxidized mono-, di-, or polyesters, mono-, di-, or poly acetals containing at least one cycloaliphatic 5-membered or 6-membered ring, to which at least two 1,2-epoxide groups are linked.
A widely used class of polyepoxides which can be used in the present invention are the epoxy polyethers obtained by reacting a halogen containing epoxide or dihalohydrin, such as epichlorohydrin, epibromohydrin, 3-chloro-1,2-epoxyoctane, and the like with either a polyhydric phenol or a polyhydric alcohol.
The process of this invention can be carried out with or without a solvent at a temperature in the range of from about 80 degrees C. to about 200 degrees C. at a pressure in the range of from about atmospheric to about 50 atmospheres.
The amounts of the cationic catalysts useful in the polymerization of oxazolines and in the copolymerization of oxazolines with epoxy resins may be in the range of 0.1 to about 5% by weight of catalyst based on the weight of the monomer or monomers. The polymerizations can be carried out by using either the solid catalyst which generally dissolves in the liquid oxazolines or solutions of catalyst in solvents such as alcohols, dialkyl ketones, linear and cyclic ethers and the like.
The process of this invention is further illustrated in the following representative examples.
Liquid benzyl oxazoline (Formula I wherein R is benzyl) (10 g) and 0.2 g of lithium fluoborate were mixed and heated at 120 degrees C. for one hour during which time the liquid benzyl oxazoline polymerized to give a solid polymer which was soluble in dimethyl formamide and N-methyl pyrrolidone. The Tg by DSC (Differential Scanning Calorimetry) for this polymer was found to be 69 degrees C. and 10% weight loss in nitrogen by TGA (Thermo Gravimetric Analysis) occurred at 358 degrees C.
A bis-oxazoline of Formula II in which R' is m-phenylene (6.5 g) was melted and maintained at 160 degrees C. and to this was added 0.10 g of lithium fluoborate which was dissolved in 0.3 ml of methanol and the resulting mixture was stirred rapidly. The gelation of the resulting mixture occurred within one minute to give a solid polymer which was found to be immiscible in dimethyl formamide and N-methyl pyrrolidone. The Tg for this polymer by DSC was found to be 81 degrees C. and 10% weight loss in nitrogen by TGA occurred at 374 degrees C. for the polymer.
A mixture of 2.5 g of an oxazoline of Formula I in which R is ethyl, 0.5 g of the bis-oxazoline described in Example 2 and 0.05 g of lithium fluoborate was prepared at room temperature and heated at 120 degrees C. for one hour during which time solid polymer formed. The Tg for the polymer by DSC was found to be 40.3 degrees C. and 10% weight loss in nitrogen by TGA occurred at 388 degrees C.
The procedure of Example 3 was followed using 2.5 g of the benzyl oxazoline of Example 1, 0.35 g of the bis-oxazoline of Example 2 and 0.05 g of lithium fluoborate. The resulting polymer was found to have a Tg of 64.1 degrees C. and 10% weight loss occurred at 355 degrees C.
To a mixture of 2 g of the bis-oxazoline described in Example 2 and 10 g of liquid diglycidyl ether of Bisphenol-A (epoxy equivalent weight of 190) was added 0.2 g of lithium fluoborate dissolved in 0.5 g of methanol. The methanol was stripped from the mixture and the resulting material was divided into two parts. One part was stored at room temperature and the other part was heated at 150 degrees C. The part stored at room temperature did not polymerize until about 5 hours standing, whereas, the heated mixture polymerized within about 15 minutes to give a solid polymer which was found to be insoluble in solvents such as dimethyl formamide, N-methyl pyrrolidone, and the like. The Tg of the polymer obtained by heating was found by DSC to be 65.2 degrees C. and 10% weight loss in nitrogen by TGA occurred at 355 degrees C.
Claims (9)
1. The process for the homopolymerization of an oxazoline comprising carrying out the homopolymerization at a temperature in the range of from about 80° C. to about 200° C. at a pressure in the range of from about atmospheric to about 50 atmospheres in the presence of a catalyst which is a cationic complex of an alkali or al alkaline earth metal.
2. The process of claim 1 wherein the oxazoline is one conforming to Formula I or II ##STR4## wherein R represents hydrogen, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 12 carbon atoms, an alkaryl group having from 7 to 20 carbon atoms, an alkyl ether group having from 1 to 20 carbon atoms or an aryl ether group having from 6 to 26 carbon atoms and R' represents an alkylene group having from 1 to 20 carbon atoms, an arylene group having from 6 to 12 carbon atoms or an alkylene ether group having from 2 to 20 carbon atoms.
3. The process of claim 2 wherein the catalyst is one of Formula M(X)n wherein M represents an alkali metal or an alkaline earth metal, X represents BF4, PF6, BPh4, ClO4, AsF6 and SbF6, and n represents 1 or 2 depending on the valence of M.
4. The process of claim 3 wherein the catalyst is present in from 0.1 to about 5% by weight based on the weight of the oxazoline.
5. The process of claim 4 wherein the oxazoline is one of Formula I in which R is benzyl and the catalyst is lithium fluoborate.
6. The process of claim 4 wherein the oxazoline is of Formula II in which R' is m-phenylene and the catalyst is lithium fluoborate.
7. The process of claim 4 wherein the oxazoline is a mixture of one of Formula I in which R is ethyl and one of Formula II in which R' is m-phenylene and the catalyst is lithium fluoborate.
8. The process of claim 4 wherein the oxazoline is a mixture of one of Formula I in which R is benzyl and one of Formula II in which R' is m-phenylene and the catalyst is lithium fluoborate.
9. The process of claim 4 wherein the oxazoline is one of Formula II wherein R' is m-phenylene and the catalyst is lithium fluoborate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/765,634 US4658011A (en) | 1985-08-15 | 1985-08-15 | Polymerization of oxazoline using alkali or alkaline earth metal complex catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/765,634 US4658011A (en) | 1985-08-15 | 1985-08-15 | Polymerization of oxazoline using alkali or alkaline earth metal complex catalyst |
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| Publication Number | Publication Date |
|---|---|
| US4658011A true US4658011A (en) | 1987-04-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/765,634 Expired - Fee Related US4658011A (en) | 1985-08-15 | 1985-08-15 | Polymerization of oxazoline using alkali or alkaline earth metal complex catalyst |
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| US (1) | US4658011A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993020128A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Process for polymerizing cyclic iminoethers |
| US5616659A (en) * | 1994-01-19 | 1997-04-01 | Southwest Research Institute | Low flammability thermoset polymers |
| US5618896A (en) * | 1994-05-06 | 1997-04-08 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
| US5644006A (en) * | 1994-10-14 | 1997-07-01 | Southwest Research Institute | High strength thermoset copolymers incorporating modified bisoxazoline monomers. |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542699A (en) * | 1969-04-02 | 1970-11-24 | Allied Chem | Crosslinked polymers of 2-hydroxyalkyl or alkenyl oxazines and oxazolines |
| US4365056A (en) * | 1980-09-25 | 1982-12-21 | Chemische Werke Huls Ag | Process for producing 2-(C1 to C3 alkyl)-Δ2 -oxazoline copolymers |
-
1985
- 1985-08-15 US US06/765,634 patent/US4658011A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3542699A (en) * | 1969-04-02 | 1970-11-24 | Allied Chem | Crosslinked polymers of 2-hydroxyalkyl or alkenyl oxazines and oxazolines |
| US4365056A (en) * | 1980-09-25 | 1982-12-21 | Chemische Werke Huls Ag | Process for producing 2-(C1 to C3 alkyl)-Δ2 -oxazoline copolymers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993020128A1 (en) * | 1992-03-27 | 1993-10-14 | Henkel Kommanditgesellschaft Auf Aktien | Process for polymerizing cyclic iminoethers |
| US5616659A (en) * | 1994-01-19 | 1997-04-01 | Southwest Research Institute | Low flammability thermoset polymers |
| US5618896A (en) * | 1994-05-06 | 1997-04-08 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
| US5670590A (en) * | 1994-05-06 | 1997-09-23 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
| US5644006A (en) * | 1994-10-14 | 1997-07-01 | Southwest Research Institute | High strength thermoset copolymers incorporating modified bisoxazoline monomers. |
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